Process for preparing mixed polyalkylene glycol phosphorus compounds

ABSTRACT

Mixed polyalkylene glycol polyphosphorus compounds containing both phosphite and vinyl phosphate linkages are prepared by reacting certain polyalkylene glycol polyphosphites with less than a stoichiometric amount of a halogenated carbonyl compound.

United States Patent 1 1 Shim [4 1 Apr. 15, 1975 PROCESS FOR PREPARINGMIXED POLYALKYLENE GLYCOL PHOSPHORUS COMPOUNDS [60] Division of Ser. No.166,289, July 26, 197i, Pat. No. 3,798,290, which is acontinuation-in-part of Ser. No. 86,313, Nov. 2, 1970, Pat. No.3,819,750, which is a continuation-in-part of Ser. No. 63,262, Aug. 6,1970, abandoned.

[52] US. Cl 260/969; 260/2.5 AJ; 260/929 [51] Int. Cl. C07f 9/08; C08g22/44 [58] Field of Search 260/969, 929

[56] References Cited UNITED STATES PATENTS 3,328,493 6/1967 Larrison260/929 Primary ExaminerAnton I-I. Sutto i 1 ABSTRACT Mixed polyalkyleneglycol polyphosphorus compounds containing both phosphite and vinylphosphate linkages are prepared by reacting certain polyalkylene glycolpolyphosphites with less than a stoichiometric amount of a halogenatedcarbonyl compound.

5 Claims, No Drawings PROCESS FOR PREPARING MIXED POLYALKYLENE GLYCOLPHOSPHORUS COMPOUNDS RELATED APPLICATIONS This is a division ofapplication Ser. No. 166,289. filed July 26, 1971, issued as U.S. Pat.No. 3,798,290 on Mar. 19, 1974, which in turn is a continuation-inpartof application Ser. No. 86,313, filed Nov. 2, 1970, issued as U.S. Pat.No. 3,819,750 on June 25, 1974, which in turn is a continuation-in-partof application Ser. No. 63,262, filed Aug. 6, 1970 by Kyung Sup Shim,and now abandoned.

BACKGROUND OF THE DISCLOSURE 1n the polyurethane field, increasedinterest is being shown in compounds which can be added to thepolyurethane polymers to act as fire retardant agents. Particularinterest is being shown in compounds which have functional groupsreactive with the polyol or polyisocyanate used in preparing thepolyurethane so that the fire retardant agent can be copolymerized intothe polymer chain. One such group of reactive flame retardants are thepolyalkylene glycol phosphites such as those described in U.S. Pat. No.3,009,939. However, these materials, due to their high OH numbers andcrosslinking tendency, are unsuitable for use in flexible urethanefoams. ln U.S. Pat. Nos. 3,081,331 and 3,142,651, there is disclosed amethod of forming polyalkylene glycol polyphosphites having up tophosphite groups in the polymer chain by reacting a trialkyl phosphitewith a polypropylene glycol in a molar ratio of 2.1 to 2.5 moles ofglycol per mole of phosphite. These materials are also unsuitable foruse in flexible urethane foams as a result of their high OH numbers andtheir tendency to crosslink.

Another attempt at employing reactive flame retardants, described inU.S. Pat. Nos. 3,142,651 and 3,092,651, involves the use ofpolypropylene glycol poly-hydrogenphosphonates produced by a thermalpolymerization. Likewise, polyalkylene glycol hydrogen polyphosphonateshave also been produced by transesterifying a secondary hydrogenphosphonate with a polyalkylene glycol according to the procedureoutlined in British Pat. Nos. 796,446 and 1,011,118. However, many ofthese materials have relatively high acidity, causing them to react withand thereby deactivate certain catalyst systems generally used in theformation of polyurethane polymers such, for example, as tertiary aminecompounds. The first method has the additional drawback ofcontaminationof the product by the alkylene glycol by-product, which contamination isnot easily removed.

1n order to increase the flame retardancy of some of the above describedphosphorus compounds, which have low phosphorus content, the prior arthas attempted to incorporate various halogen containing substituentsinto the above described molecules. Thus U.S. Pat. No. 3,159,605describes the reaction of halogenated methanes with these compounds,Likewise U.S. Pat. Nos. 3,131,206 and 3,328,493 describe the reaction ofchloral with them. However, these materials, like their precursors, havemany drawbacks. In particular these products have high OH numbers andlow phosphorus content thereby rendering them unsuitable as flameretardants in flexible urethane foams.

1n the above cited co-pending U.S. applications, there are disclosednovel polyalkylene glycol vinyl phosphates which are far superior asflame retardants for urethane foams, particularly flexible foam, thanany of the above described flame retardants. These vinyl phosphates,however, have one drawback. While they yield foams having excellentflame retardance and physical characteristics, they tend to discolor thecenter of the bun, thereby rendering the foam objectionable inappearance.

It is an object of the present invention to prepare novel polyalkyleneglycol polyphosphorus compounds which are suitable as flame retardantsfor urethane foams, and in particular flexible urethane foams.

It is another object of the present invention to prepare novelpolyalkylene glycol polyphosphorus compounds which, while exhibitingflame retardancy and physical properties comparable with those of theflame retardants described in the above c ed co-pending applications,yield foams having good color and appearance throughout. Furtheradvantages of the present invention will become obvious from a readingof the disclosure which follows hereinafter.

TECHNlCAL DESCRIPTION OF THE DISCLOSURE It has now been discovered that,by reacting a halogenated carbonyl compound with certain polyalkyleneglycol polyphosphites in an amount less than the stoichiometricequivalent, there is obtained a polyalkylene glycol polyphosphoruscompound having both phosphite and vinylphosphate linkages along thepolymer chain. These polyalkylene glycol polyphosphorus compounds, whenincorporated into urethane foams, yield foams having superior flameretardance, physical properties, and little if any discoloration in thebun.

The polyalkylene glycol polyphosphorus compounds of the presentinvention are polymers containing both phosphite and vinylphosphatelinkages. They are characterized by low OH numbers and acidity, a lackof the tendency to gel initially or Crosslink in the final foamedproduct, and high stability during and subsequent to the foam formingprocess. These compounds can be represented by an idealized formula asfollows:

wherein R is a polyalkylene glycol residue; R is eithe hydrogen, alkylor haloalkyl; Z and Y are each either hydrogen, halogen, or alkyl; R, isan alkyl residue from the tertiary phosphite used to produce thepolyalkylene glycol alkyl polyphosphite starting material of the presentinvention; m and n are numbers in the range between from 1 to about 25such that the sum of m+n is from about 2 to about 50, and preferablybetween about 4 to about 10. In the above formula, when any of R X and Zare an alkyl or haloalkyl group, they preferably contain from 1 to about4 carbon atoms. The term alkyl residue as designated by R, is preferablyL alkyl and most preferably methyl or ethyl. The term halogen and theprefix halo are meant to designate either chlorine or bromine. The termolya y glycol residue, designated by R, is meant to define that portionremaining after two hydroxyl groups have been removed from apolyalkylene glycol having the forwherein R" is an alkylene group offrom 2 to about carbon atoms, which is straight chained. branch chained,or a mixture thereof. and .v designates the number of repeating alkyleneether units and is normally from 2 to about 20.

The formula for the polyphosphorus compounds shown above, as will bereadily appreciated by those skilled in the art, is meant to designate amixed polymer wherein the phosphite and phosphate linkages are randomlydispersed along the polymer chain. Furthermore, it is understood thatthe formula encompasses mixtures of polymers having an average chainlength of m+n wherein m and n each represent an average value of thenumber of phosphite and phosphate linkages contained in this mixturerather than just a single pure compound.

The compounds of the present invention are produced by reacting ahalogenated carbonyl compound with a polyalkylene glycol alkylpolyphosphite which has an idealized formula as follows:

wherein R, R,, m and n are as described as above. This polyphosphite, inturn, is formed by transesterifying a tertiary phosphite with apolyalkylene glycol in a molar ratio of from about 1 to about 1.5 andpreferably from 1 to 1.2, moles of phosphite per mole of glycol.

The tertiary phosphite used to prepare the polyalkylene glycol alkylpolyphosphite starting material has the general formula:

HORO

wherein each R, is as defined above. The phosphites used can be chosenfrom the following: trimethyl phosphite, triethyl phosphite, tripropylphosphite, tributyl phosphite, trioctyl phosphite, dimethyl ethylphosphite, diethyl methyl phosphite, and the like. Trimethyl andtriethyl phosphite are particularly preferred, with trimethyl phosphitebeing most preferred.

The above described tertiary phosphite is transesterified with apolyalkylene glycol having the formula:

wherein R" and x are as described above. Illustrative of thepolyalkylene glycols which can be employed in the present invention arethe following: diethylene glycol, triethylene glycol, dipropyleneglycol, tripropylene glycol, tributylene glycol, polyethylene glycolswherein the average number of ether units is 2, polypropylene glycolswherein the average number of ether units is 14, trihexylene glycol andthe like. Particularly preferred glycols are diethylene glycol,dipropylene glycol and tripropylene glycol. It is understood that thesepropylene glycols can be primary, secondary or mixtures thereof.

In order to form the polyphosphite starting materials of the presentinvention, the tertiary phosphite and the polyalkylene glycol must bereacted in critical proportions. Thus, the phosphite should be presentin an amount from about 1 to about 1.5 moles per mole of the glycol. Thepreferred range for this preparation is from about 1 to about 1.2 molesof phosphite per mole of glycol. 1f the glycol is reacted in quantitiesgreater than 1 to 1 with the phosphite, the product will containprimarily the undesirable mono, di, tri and tetraphosphites and, moreimportantly, will have a substantial amount of free alkylene hydroxylgroups attached to the phosphite group.

The above disclosed transesterification reaction is normally conductedby mixing the phosphite and glycol in the presence of any of the wellknown transesterification catalysts. Particularly useful catalysts arethe alkali metal alcoholates and phenolates such as sodium methylate,sodium decylate, sodium phenolate, and the like. These catalysts arenormally employed in an amount from about 0.01 to about 10 percent, byweight, of the entire reactant mixture. The reaction temperature shouldinitially be kept below the boiling point of the lowest boiling reactantin order to avoid the loss of that reactant. Although the reaction canbe conducted at room temperature, i.e. 20C., it is preferred to conductit as close to the upper limit as possible in order to increase the rateof reaction. Thus, in the case where trimethyl phosphite is employed asthe tertiary phosphite, the reaction temperature is preferably withinthe range of,80C. to C. and should not be allowed to rise above C. untilat least one R, group on each of the phosphite molecules has beenreplaced with a polyalkylene glycol. This can normally be determined bymonitoring the amount of methanol which has been evolved.

While the reaction can be run to completion at those temperature ranges,it has been found to be advantageous to raise the temperature after thisinitial replacement of one of the R groups on the starting phosphiteupto a limit of about 200C. and most preferably up to about C. As statedabove, the point at which the temperature should be raised can bedetermined by monitoring the amount of by-product alkanol produced.Thus, when one mole of trimethyl phosphite 15 being transesterified, thereaction temperature can be raised after one mole of methanol has beenevolved. The transesterification is completed when two moles of methanolhave been evolved. The degree of polymerization of the polyphosphite canbe controlled to an extent by varying the time of the reaction.Furthermore, the polymer length can be monitored by measuring theviscosity buildup during the reaction according to well knowntechniques.

The transestcrification reaction can optionally be carried out in thepresence of an inert solvent, however, such solvent is not required forthe practice of the present invention. The term inert solvent is meantto designate any solvent which does not react with the startingmaterials or products of the present invention. Suitable solventsinclude the alkylated benzenes such as ethyl benzene, diethyl benzene,toluene. the xylenes, and the like.

The polyalkylene glycol alkyl polyphosphites produced by the processdescribed above is then reacted with a halogenated carbonyl compoundhaving the formula:

where R, Z and Y are as defined above and X is bromine or chlorine.These carbonyl compounds can be illustrated by the following: chloral,bromal, l,l,ltrichloroacetone, l,l;l-tribromoacetone, hexachloroacetone,hexabromoacetone, pentachloroacetone, monochloroacetone,monobromoacetone, dichloroacetaldehyde, dibromoacetaldehyde,chloroacetaldehyde, bromoacetaldehyde, chloromethyl ethyl ketone,dichloromethyl ethyl ketone, trichloromethyl ethyl ketone, bromomethylethyl ketone and the like. Preferred carbonyl compounds are chloral,bromal, monochloroacetone, monobromoacetone. trichloroacetone,tribromoacetone, pentachloroacetone, hexachloroacetone,dichloroacetaldehyde and chloromethyl ethyl betone. Particularlypreferred compounds for use in the present invention are chloral,bromai, monochloroacetone and monobromoacetone.

The carbonyl compound is reacted with the polyphosphite in less than astoichiometric quantity. The term, stoichiometric quantity as usedherein, is meant to designate the molar equivalent of phosphite groupsin the polyphosphite. By employing less than this quantity, the productwill contain unreacted phosphite groups, which stabilize the urethanefoam into which it has been incorporated against changes in color. Whileemploying any amount of carbonyl compound less than a stoichiometricquantity will have a color stabilizing effect, the optimum results canbe achieved by balancing the flame retardant properties of the vinylphosphate with the stabilizing properties of the phosphite. The normalrange for most foam applications is from about 0.1 to about 0.9 moles ofcarbonyl compound per mole of phosphite group. The most preferred rangefor flexible urethane foams is from about 0.6 to about 0.9 moles ofcarbonyl compound per mole of phosphate group.

The carbonyl compound can be reacted with the polyphosphite over a widetemperature range. Normally temperatures from about 0 to about 150C. areemployed, with the preferred range being from about to about 85C. Thereaction can be monitored by determining the amount of alkyl halideby-product formed. Thus, when 0.6 molar equivalents of carbonyl compoundare used, the reaction is completed when 0.6 moles of alkyl halide haveevolved.

The reaction with the carbonyl compound is preferably carried out in thepresence of a solvent or diluent although this is not necessary to theinvention. The solvent helps to control the temperature of the reaction,which is very exothemic in nature, and thereby, eliminates the necessityof cooling the reactants to maintain the proper reaction temperature.The solvent or diluent should be non-reactive with respect to both thestarting materials and the desired products, and should be miscibletherewith. Illustrative of suitable solvents are benzene, xylene,ethylbenzene, diethylbenzene. various alkanes. and the like.

The novel compounds of the present invention are characterized by theirability to copolymerize with polyisocyanates employed in formingpolyurethanes. by their relatively low OH numbers and acidity, by theirhigh phosphorus content, and by their high flame retardancy andstabilizing characteristics in the final foams. These compounds cancompletely replace the polyols normally employed in forming the foams orthey can be used in combination with the polyols, thereby yielding foamswith greatly improved flame resistance. Since they react in the foamforming process, their residues are chemically bonded into the foam.thereby giving them high permanance, even upon high temperature aging.The acid numbers of the compounds of the present invention are normallybelow about 2 millegrams of KOH per grams of the polyalkylene glycolpolyphosphorus compound. This low acidity makes these compoundsrelatively unreactive toward the polymerization catalysts employed inproducing the polyurethane foams. The vinyl phosphate groups in thesecompounds reduces the concentration necessary to achieve a flameresistant foam, while the phosphite group stabilizes the foam againstdiscoloration. As mentioned above, these compounds have relatively lowOH numbers as compared to the prior art flame retardants and, therefore,can be used in flexible urethane foams without materially affecting thephysical properties of such foams. By the term relatively low OHnumbers, it is meant to designate OH numbers below about and preferablybelow 100.

The compounds of the present invention are further characterized by thefact that they are substantially linear polymers when compared to thosedisclosed in the prior art. This result, at least in part, from the factthat the intermediate polyalkylene glycol alkyl polyphosphites used tomake the present compounds contain primarily alkyl side chains attachedto the phosphite groups. Consequently, the labile halogen released bythe attacking carbonyl compound will preferentially react with the alkylside chain rather than with the glycol linking groups. Thus, it has beenobserved that the by-product formed by the addition of the carbonylcompound to the polyphosphite intermediate used herein is the alkylhalide rather than the halogenate polyether alcohol which would resultfrom attack on the polyalkylene glycol. Since the phosphite alkyl groupis attacked preferentially there is little or no depolymerization.

An additional advantage inherent in the present invention is the factthat the alkyl halide by-product can easily be separated from thedesired final product whereas a halogenated polyether alcoholby-product, such as would be formed when using the polymers described inUS. Pat. No. 3,328,493, cannot be easily separated due to its higherboiling point. Furthermore, the necessity for separating a halogenatepolyether alcohol by-product such as would be formed by US. Pat. No.3,328,493 is manifest since it is a monofunctional alcohol which wouldseriously impair, if not destroy, the foam forming ability of theurethane foam mix.

i lene The compounds of the present invention, when employed insufficient quantity, will yield a selfextinguishing polyurethane foam.This characteristic is particularly important in the area of flexiblefoams due to the wide use of such foams in hospitals, homes andautomobiles. Normally, the compounds of the present invention can beemployed in amounts of from about to about 30 percent, by weight, of theentire foam forming mixture to yield self-extinguishing flexible foams.Preferably they are employed in amounts from 10 to percent, by weight.of the entire mixture. It is understood, however, that this amount willvary depending upon the particular foam being used, and that therequired proportions can easily be determined with a minimum amount ofblending work.

While the compounds of the present invention are primarily intended foruse in urethane foams, it is contemplated that they can also be used ina wide variety of polymeric systems. Illustrative of these systems are:polyesters, polyolefms, cellulose ethers and esters, urethane coatingsand elastomers, polymethyl methacrylates, polyvinyl chlorides, and manyothers. Furthermore. the compounds of the present invention can also beemployed in combination with any of the known flame retardants in foamsor polymeric systems.

The polyurethane foams within which the flame retardants described abovethe incorporated are well known in the art. They are produced by thereaction of a dior polyisocyanate and a dior polyhydroxy (polyol)compound in the presence of a blowing agent and a catalyst. The foamscan be made by any of the basic techniques used in foam formation; i.e.,the prepolymer technique, the semi-prepolymer technique or the one-shotprocess. These techniques are well known and described in thepolyurethane art.

As examples of organic diand polyisocyanates which can be employed tomake the polyurethane foams there can be employedtoluene-2,4-diisocyanate; toluene-2,6-diisocyanate; 4-methoxyl,3-phenylene diisocyanate; diphenyl methane-4,4'-diisocyanate; 4-chlorol ,3-phenylene-diisocyanate; 4-isopropyll ,3-phenylene-diisocyanate; 4-ethoxyl ,3-phenylenediisocyanate;2,4-diisocyanate-diphenylether; 3,3- dimethyl-4,4'diisocyanate-odiphenylmethane; mesitydiisocyanate; durylene diisocyanate; 4,4- methylene-bis(phenylisocyanate); benzidine diisocyanate; o-nitrobenzidinediisocyanate; 4,4-diisocyanatedibenzyl; 3,3-bitolylene-4,4-diisocyanate; 1,5- naphthalene diisocyanate;tetramethylene diisocyanate; hexamethylene diisocyanate; decamethylenediisocyanate; toluene-2,4,6-triisocyanate; tritelylmethanetriisocyanate; 2,4,4-triisocyanatodiphenyl ether; the reaction productof toluene diisocyanate with trimethylolpropane; and the reactionproduct of toluene diisocyanate with 1,2,6-hexanetriol.

Alternatively, as the polyisocyanate there can be used prepolymers madeby reacting one or more of the above polyisocyanates with a diorpolyhydroxy compound such as a polyester having terminal hydroxylgroups, a polyhydric alcohol, glycerides or hydroxy containingglycerides, etc. These prepolymers should have terminal isocyanategroups and, to insure their presence, it is frequently desirable toemploy an excess of 5% or more of the polyisocyanate in forming theprepolymer. Typical examples of such prepolymers having isocyanate endgroups are those formed from toluene diisocyanate and polyhydroxycompounds. In most cases, a mixture of of the 2,4-isomer and 20% of the2,6-isomer of toluene diisocyanate is employed in making theseprepolymers. Thus, there can be used the prepolymers resulting from thereaction between tolucne diisocyanate and caster oil, blown tung oil,blown linseed oil or blown soya oil, and of toluene diisocyanate and thepolyester of ethylene glycol, propylene glycol and adipic acid.

Examples of suitable polyols are polyethylene glycol, polypropyleneglycoles, ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, tripropylene glycol,1,4-butanediol, thiodiglycol, glycerol, trimethylolethane,trimethylolpropane, ether triols from glycerine and propylene oxide,other containing triols from 1,2,6-hexanetriol and propylene oxide,sorbitol-propylene oxide adducts, pentaerythritol-propylene oxideadducts, trimethylol phenol, oxypropylated sucrose, triethanolamine,pentaerythritol, diethanolamine, castor oil, blown linseed oil, blownsoya oil, N,N,N,N-tetrakis(2-hydroxyethyl) ethylenediamine,N,N,N,N-tetrakis(Z-hydroxypropy]) ethylenediamine,N,N,N',N",N",-pentakis(2- hydroxypropyl) diethyl triamine,N,N,N,N",N"-pentakis(2-hydroxyethyl) diethylene triamine, mixed ethyleneglycol-propylene glycol adipate resin, polyethylene adipate phthalateand polyneopentylene sebacate.

In preparing the foamed polyurethanes there can be used any of theconventional basic catalysts such, for example, as N-methyl morpholine,N-ethyl morpholine, l,2,4-trimethylpiperazine, trimethyl amine, triethylamine, tributyl amine and other trialkyl amines, the esterificationproduct of adipic acid and diethylethanolamine, triethyl amine citrate,3-morpholinopropionamide, l,4-bis(2-hydroxypropyl)-2-methylpiperazine,Z-diethylaminoacetamide, 3-diethylaminopropionamide,diethylethanolamine, triethylenediamine, N,N,N,N-tetrakis(2-hydroxypropyl) ethylenediamine, N,N-dimethylpiperazine,N,N-dimethylhexahydroaniline, tribenzylamine and sodium phenolate. Also,

applicable are tin compounds, e.g. hydrocarbon tin acrylates such asdibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate,tributyltin monolaurate, dimethyltin diacetate, dioctyltin diacetate,dialauryltin diacetate, dibutyltin malcate, hydrocarbon tin alkoxides,e.g. dibutyltin diethoxide, dibutyltin dimethoxide, diethyltindibutoxide as well as other tin compounds, e.g. octylstannoic acid,trimethyltin hydroxide, trimethyltin chloride, triphenyltin hydroxide,trimethyltin chloride, triphenyltin hydride, triallyltin chloride,trioctyltin fluoride, dibutyltin dibromide, bis-(carboethoxymethyhtindiiodide, tributyltin chloride, trioctyltin acetate, butyltintrichloride, octyltin tris-(thiobutoxide dimethyltin oxide, dibutyl tinoxide, dioctyltin oxide, diphenyltin oxide, stannous octanoate, andstannous oleate.

Any of the conventional surfactants can be used in amounts of 1% orless, e.g. 0.2% by weight of the composition. The preferred surfactantsare silicones, e.g. polydimethyl siloxane having a viscosity of 3 tocentistokes, triethoxydimethyl polysiloxane, molecular weight 850copolymerized with a dimethoxypolyethylene glycol having a molecularweight of 750.

The foaming reaction can be carried out by adding water to the polyolprior to or simultaneously with the addition of the polyisocyanate.Alternatively, foams can be prepared by the use of a foaming or blowingagent. These are usually a liquefied, halogen substituted alkane such.for example. as methylene chloride. Especially preferred are thosehalogen substituted alkanes having at least one fluorine atom in theirmolecules such as trichlorofluoromethane. dichlorodifluoromethane.dichloromethane. ehlorodifluoromethane. dichlorotetrafluoroethane. Inusing these blowing agents, they are uniformly distributed in either thepolyol reactant or the polyisoctanate reactant whereupon the reactantsare mixed permitting the temperature of the mixture to rise during theensuing reaction above the boiling point of the liquefied gas so as toproduce a porous polyurethane. it should be noted that foaming may alsobe affected by combining the use of a blowing agent with the addition ofwater to the polyol.

EXAMPLE I A three-necked flask equipped with a mechanical stirrer.thermometer and distilling head is charged with 268g. (2.0 moles) ofdipropylene glycol, 272.8g. (2.2 moles) of trimethyl phosphite and 1.0g.of sodium methoxide. The reactants are then heated slowly to 110C. Atotal of 111g. of volatiles are removed and the reaction mixture is thenstripped at 108C with aspirator vacuum. The mixture is subsequentlycooled and 200 ml. of benzene is added. The reactant mixture is furthercooled by means of an ice bath and 176.4g. (1.2 moles) of chloral isadded at a rate sufficient to maintain the pot temperature below aboutC. The temperature is then raised to 80C and aspirator vacuum applied.After the volatiles have been removed. 480.4 grams of a viscous liquidproduct is obtained. The product is neutral and gives the followinganalysis:

()H number 2s P/1 10.2 (theoretical 10.3%) C1 20.7 (theoretical 23.674)

Infrared analysis shows that the product contains both vinylphosphateand phosphite groups.

EXAMPLE 2 The procedure of Example 1 is repeated except that 212g (2.0moles) of diethylene glycol is substituted for the dipropylene glycol.The resultant product is a viscous oil having a slightly higher P & CIcontent than that of Example l.

EXAMPLE 3 The procedure of Example 1 is again repeated except that 384grams (2.0 moles) of tripropylene glycol is substituted for thedipropylene glycol. The resultant product has a slightly lower P and Clcontent than the product of Example 1.

In like manner to the above examples. bromal. monoch-loroacetone,monobromoacetone, trichloroacetone, tribromoacetone, pentachloroacetone.pentabromoacetone, hexachloroacetone, hexabromoacetone and chloromethylethyl ketone give good results when substituted for the chlorol inExample 1.

EXAMPLE 4 A gallon reactor fitted with a vacuum distilling column wascharged with approximately 26.2 kg. (195 moles) of dipropylene glycol,26.6 kg. (214 moles) of trimethyl phosphite and 250 grams of a 25%solution of sodium methylate. The pot temperature was raised from 20C toC over a period of 15 minutes. The temperature was again raised from 80Cto about 102C over 30 minutes and maintained in the range from l00-l 10Cfor 45 minutes. during which time a vacuum of 37 mm. was applied.Thereafter about 30 kg. of benzene solvent was added and the temperaturewas reduced to 54C. The stepwise addition of 17.4 kg. l 18 moles) ofchloral was then conducted over a period of 25 minutes while thetemperature was allowed to climb to about 69C. The reactant mixture wasallowed to stand for approximately minutes and then vacuum was appliedand the temperature was raised to 85C over a period of 60 minutes. Thefinal yield was 46.5 kg. of yellow oil having the following properties:

n"""",, 1.4774 Acid No. 0.14 mg KOH/g sample OH N0. 20 mg KOH/g sampleCL 23.0; P 9.956?

EXAMPLE 5 A polyurethane foam was prepared by employing the followingformulation:

propylated glycerol (3000 mol. wt.) 200 g A polyphosphorus compoundprepared according to the procedure of Example 4. 30 g siliconesurfactant 1.8 g Water 8.0 N-ethylmorpholine 0.40 g Z-(diethylamine)ethyl ether 0.35 g 5091' stannous octoate in dioctyl phthalate 0.80 gtoluene diisocyanate 102.3 g

(80/20 isomers) The resultant product was a flexible foam having goodcolor and odor and was self-extinguishing upon dry heat aging at C for22 hours.

What is claimed is:

l. The process of preparing polyalkylene glycol polyphosphoruscompositions characterized by OH numbers below about and having theformula:

0 0R I! I HORO P ORO P 0R0 H /Y R' -c=c wherein R is the residue of apolyalkylene glycol having the formula:

m n is in the range from about 2 to about 50; comprising reacting (a) apolyalkylene glycol alkyl phosphate of the formula;

12 about 0 10 about C.

2. The process of claim 1 wherein said carbonyl compound is reacted withsaid polyphosphite in a range from about 0.5 to about 0.9 moles ofcarbonyl compound per mole of polyphosphite.

3. The process of claim 1 wherein said polyalkylene glycol alkylpolyphosphite is selected from the group consisting of diethylene glycolalkyl polyphosphites, dipropylene glycol alkyl polyphosphites andtripropylene glycol alkyl polyphosphites.

4. The process of claim 1 wherein the halogenate carbonyl compound isselected from the group consisting of chloral. bromal monochloroacetone,monobromoacetone, trichloroacetone, tribromoacetone. hexachloroacetone,hex-abromoacetone, dichloroacetaldehyd'e. pentachloroacetone andchloromethyl ethyl betone.

5. The process of claim 2 wherein said polyalkylene glycol polyphosphiteis a dipropylene glycol methyl polyphosphite and said carbonyl compoundis chloral.

UNITED STATES PATENT AND TRADEMARK OFFICE CETIFTQATE 0F CO RECTION gPATENT NO. 5,878,270

DATED April 15, 1975 INVENTOR(S) Kyung S. Shim it is certified rhaterrorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column A, line #7, change those to these Column 5, line 51, change"betone" to ketone Column 5, line 52, change "phosphate" to phosphiteColumn 6, line 25, change "millegrams" to milligrams Q Column 6, line25, change grams to gram Column 8, line A l, change malcate to maleateColumn 9, line 5, change dichloromethane to dichloromonof luoromethaneColumn 12, Claim l, line 16, change be" to ke- 9 Signed and Scaled thisnineteenth D y of Augusl1975 [SEAL] Aff'Sf. O

RUTH- C. MASON C. MARSHALL DANN Arresting ()jfrcer (ummissr'nnvruj'Parenls and Trademarks

1. THE PROCESS OF PREPARING POLYALKYLENE GLYCOL POLPHOSPHORUSCOMPOSITIONS CHARACTERIZED BY OH NUMBERS BELOW ABOUT 150 AND HAVING THEFORMULA:
 2. The process of claim 1 wherein said carbonyl compound isreacted with said polyphosphite in a range from about 0.5 to about 0.9moles of carbonyl compound per mole of polyphosphite.
 3. The process ofclaim 1 wherein said polyalkylene glycol alkyl polyphosphite is selectedfrom the group consisting of diethylene glycol alkyl polyphosphites,dipropylene glycol alkyl polyphosphites and tripropylene glycol alkylpolyphosphites,
 4. The process of claim 1 wherein the halogenatecarbonyl compound is selected from the group consisting of chloral,bromal, monochloroacetone, monobromoacetone, trichloroacetone,tribromoacetone, hexachloroacetone, hexabromoacetone,dichloroacetaldehyde, pentachloroacetone and chloromethyl ethyl betone.5. The process of claim 2 wherein said polyalkylene glycol polyphosphiteis a dipropylene glycol methyl polyphosphite and said carbonyl compoundis chloral.